TWI735015B - Polysiloxane resin, coating composition containing the same and application thereof - Google Patents

Abstract

The present invention provides a polysiloxane resin, which comprises a reaction product of the following: (a) a nonlinear polysiloxane oligomer, which has a C_1-3 alkoxyl or hydroxyl group and a weight average molecular weight of about 500-6000, (b) a linear polysiloxane oligomer, which has formula (II):

, and (c) a siloxane monomer, wherein R³ , R⁴ and m are those as defined in the specification. The present invention also provides a coating composition comprising the aforementioned polysiloxane resin.

Description

Polysiloxane resin, coating composition containing it and application thereof

The present invention relates to a polysiloxane resin and a coating composition containing the polysiloxane resin and its application.

Polysiloxane resin has properties such as optical transparency, low thermal conductivity, low toxicity, electrical insulation, and chemical resistance, and is widely used in various fields, such as coatings, adhesives, etc.

Polysiloxane resins are based on silicon-oxygen bonds (-Si-O-) and can be synthesized from various silicon-containing monomers and oligomers. By selecting the starting material and controlling the structure (such as the degree of crosslinking or divergence) and molecular weight of the polysiloxane resin, polysiloxane resins with different properties can be provided, such as liquid silicone oil and flexible polysilicon Oxyane resins, even rigid polysiloxane resins. However, the above properties are often not compatible. For example, polydimethylsiloxane (PDMS) is a linear polysiloxane resin with good flexibility, but it is used for high-temperature baking or long-term exposure. At high temperatures, surface cracks may occur. Polysiloxane resins with good rigidity are often not resistant to bending and are susceptible to stress and cracks or breaks.

In view of this, various polysiloxane resins have been continuously developed in the technical field to meet different needs.

The present invention provides a novel polysiloxane resin. The polysiloxane resin of the present invention has properties such as hardness, toughness, flexibility, bending resistance, weather resistance, heat resistance, chemical resistance, etc., so it is more applicable than the polysiloxane resin of the prior art Provide convenience in application on different occasions.

(II)，及 (c)矽氧烷單體， 其中，各R³ 可相同或不同，各自獨立為甲基或苯基；各R⁴ 可相同或不同，各自獨立為H、甲基或乙基；m為2至20之整數。An object of the present invention is to provide a polysiloxane resin, which contains the reaction product of the following: (a) Non-linear polysiloxane oligomer (also referred to as "oligomer A"), which has C _1-3 alkoxy or hydroxyl groups, and have a weight average molecular weight of about 500-6000, (b) linear polysiloxane oligomer (also referred to as "oligomer B"), which has the formula (II):

(II), and (c) Silicone monomers, wherein each R ³ may be the same or different, and each independently is a methyl group or a phenyl group; each R ⁴ may be the same or different, and each independently is H, methyl or ethyl Base; m is an integer from 2 to 20.

Another object of the present invention is to provide a coating composition containing the above-mentioned polysiloxane resin.

Another object of the present invention is to provide the use of the above-mentioned polysiloxane resin or coating composition, which is used as an intermediate layer or top coat of metal coils, coatings for glass substrates, or coatings for solar backplanes.

Another object of the present invention is to provide a substrate comprising a coating layer composed of the above-mentioned polysiloxane resin or coating composition.

In order to make the above objectives, technical features, and advantages of the present invention more obvious and understandable, some specific embodiments are described below in detail.

In order to facilitate the understanding of the disclosure stated in this article, a number of terms are defined below.

The term "non-linear" means branched, networked, dendritic, star-shaped, waterfall-shaped, or other shapes that are not linear.

或

)的有機基團。在本發明之一些實施態樣中，較佳係使用末端具有環氧基的有機基團。The term "organic group with epoxy group" refers to having one or more epoxy functional groups (

or

) Of the organic group. In some embodiments of the present invention, it is preferable to use an organic group having an epoxy group at the end.

The term "alkyl" means a saturated straight or branched chain hydrocarbon group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 4 carbon atoms, particularly preferably having 1 to 3 carbon atoms; examples thereof include (But not limited to): methyl, ethyl, n-propyl and isopropyl.

The term "about" means the acceptable error of a specific value as determined by a person familiar with the art, and it depends in part on how the value is measured or measured.

Unless otherwise specified, the "molecular weight" or "average molecular weight" used in this specification means the weight average molecular weight (Mw.), and the unit is expressed in grams/mole.

Each aspect and each embodiment of the present invention disclosed in this specification can be individually combined with all other aspects and embodiments of the present invention, covering all possible combinations.

I. Polysiloxane resin The polysiloxane resin of the present invention comprises a polysiloxane resin derived from (a) a non-linear polysiloxane oligomer, (b) a linear polysiloxane oligomer, and (c) silicone The reaction product of alkane monomer.

(a) Non-linear polysiloxane oligomer ( oligomer A) The non-linear polysiloxane oligomer of the present invention has at least one C _1-3 alkoxy group or hydroxyl group bonded to silicon, It can undergo dehydration condensation reaction with (b) linear polysiloxane oligomer and (c) silicone monomer to improve the strength and flexibility of the resulting resin.

According to some embodiments of the present invention, (a) the non-linear polysiloxane oligomer has a weight average molecular weight (Mw.) of 500-6000, such as 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000 , 5000 or 6000, the polysiloxane resin of the present invention has good mechanical properties and flexibility, and the prepared coating can withstand the stress caused by the volume change when it returns to room temperature after high-temperature baking. Cracks or breaks. (A) When the weight average molecular weight of the nonlinear polysiloxane oligomer is less than 500, the surface toughness and strength of the coating are insufficient; when the weight average molecular weight is more than 6000, the coating has poor resistance to stress and the surface is easy to Cracks or breaks occur. Preferably (a) the non-linear polysiloxane oligomer may have a weight average molecular weight of 1000-5000, and more preferably may have a weight average molecular weight of 1500-4000. According to some embodiments of the present invention, the nonlinear polysiloxane oligomer has the formula (I): (R ⁵ ₃ SiO _1/2 ) _x (R ⁶ SiO _3/2 ) _y (R ⁷ O _1/2 ) _z (I) wherein R ⁵ and R ⁶ are each independently a methyl group, a phenyl group, a vinyl group or an organic group having an epoxy group or an acrylic group, and R ⁷ is a C _1-3 alkyl group (such as methyl Group, ethyl or propyl) or H; each R ⁵ may be the same or different, each R ⁶ may be the same or different, and each R ⁷ may be the same or different; x≧0, y>0, and z>0.

According to some embodiments of the present invention, x/y in the aforementioned formula (I) can be any value in the range of 0 to 10, for example, it can be 0, 0.005, 0.01, 0.02, 0.05, 0.08, 0.1, 0.15, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.5, 1.8, 2, 2.5, 3, 4, 5, 6, 7, 8, 9 or 10. x/y may preferably be 0.005 to 1.

、

、

或

。Specific implementation aspects of the above-mentioned organic groups with epoxy groups, such as but not limited to:

,

,

or

.

The above-mentioned organic groups with acrylic groups refer to those containing acrylic acid groups (CH ₂ =CH-C(=O)-) or methacrylic acid groups (CH ₂ =C(CH ₃ )-C(=O) -) The organic group.

(III) 其中： 各R¹ 可相同或不同，各自獨立為C_1-3 烷基，例如甲基、乙基或丙基； 各R⁶ 如前文所定義。According to some embodiments of the present invention, the nonlinear polysiloxane oligomer of the present invention includes structural units derived from the siloxane monomer of formula (III):

(III) Wherein: each R ¹ may be the same or different, and each independently is a C _1-3 alkyl group, such as methyl, ethyl or propyl; each R ^{6 is} as defined above.

According to some embodiments of the present invention, the siloxane monosystem of formula (III) is selected from the group consisting of the following compounds: methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxy Phenyl silane, phenyl trimethoxy silane, phenyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, γ-glycidyl ether oxypropyl trimethoxy silane, γ-glycidol Etheroxypropyl triethoxysilane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3,4-epoxycyclohexyl) ethyl triethoxy silane and its combination.

(V) 其中R⁵ 如前文所定義，較佳各R⁵ 皆為甲基，R⁸ 可相同或不同，各自獨立為C_1-3 烷氧基或-Cl。The non-linear polysiloxane oligomer of the present invention may optionally contain units derived from other monomers. According to some embodiments of the present invention, the nonlinear polysiloxane oligomer may comprise a structure derived from a siloxane monomer of formula (III) and a siloxane monomer of formula (IV) or (V) unit. (R ⁵ ) ₃ Si-O-Si(R ⁵ ) ₃ (IV)

(V) wherein R ^{5 is} as defined above, preferably each R ^{5 is} a methyl group, R ⁸ may be the same or different, and each independently is a C _1-3 alkoxy group or -Cl.

According to some embodiments of the present invention, the reactive monomer of the nonlinear polysiloxane oligomer may also include other monomers in addition to the above-mentioned monomers of formula (III), (IV) or formula (V).

According to one embodiment of the present invention, the siloxane single system of formula (IV) is selected from the group consisting of the following compounds: hexamethyldisiloxane, tetramethyldivinylbissiloxane and combination.

According to one embodiment of the present invention, the siloxane single system of formula (V) is selected from the group consisting of the following compounds: trimethylmethoxysilane, trimethylethoxysilane, trimethylchloride Silane, chloro (dimethyl) vinyl silane, and combinations thereof.

As mentioned above, x/y in the aforementioned formula (I) can be any value ranging from 0 to 10, where x/y can be understood as the formula (IV) used in the preparation of nonlinear polysiloxane oligomers Or the ratio of the silicone monomer of formula (V) to the silicone monomer of formula (III), when x/y=0, it means that the formula (IV) is not used in the preparation of nonlinear polysiloxane oligomers ) Or the siloxane monomer of formula (V). When a siloxane monomer of formula (IV) or formula (V) is used, x/y is preferably 0.005 to 1.

As mentioned above, z>0 in the aforementioned formula (I), where z>0 means that the non-linear polysiloxane oligomers are not all end-capped, leaving at least one silicon-bonded C _1-3 alkane The oxy or hydroxy group can further undergo condensation reaction with (b) linear polysiloxane oligomer and (c) siloxane monomer to improve the strength and flexibility of the resulting resin.

According to some embodiments of the present invention, (a) the amount of non-linear polysiloxane oligomer is the total of non-linear polysiloxane oligomer, linear polysiloxane oligomer and silicone monomer By weight, 0.5wt% to 15wt%, such as 0.5wt%, 0.75wt%, 1wt%, 1.5wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% , 10wt%, 11wt%, 12wt%, 13wt%, 14wt% or 15wt%, preferably 0.75wt% to 10wt%.

(II) 其中： 各R³ 可相同或不同，各自獨立為甲基或苯基； 各R⁴ 可相同或不同，各自獨立為H、甲基或乙基； m為2至20之整數，例如2、3、4、5、6、8、10、12、14、16、18或20，較佳為5至12之整數。 (b) Linear polysiloxane oligomer ( oligomer B) The linear polysiloxane oligomer of the present invention comprises a unit derived from a silicone monomer of formula (II):

(II) Wherein: each R ³ may be the same or different, and each is independently methyl or phenyl; each R ⁴ may be the same or different, and each is independently H, methyl or ethyl; m is an integer from 2 to 20, for example 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18 or 20, preferably an integer of 5-12.

Commercially available models such as Dow Corning® 3074 (molecular weight 1200-1700) or Dow Corning® 3037 (molecular weight 700-1500) sold by Dow Corning.

According to some embodiments of the present invention, (b) the linear polysiloxane oligomer has a weight average molecular weight (Mw.) of 500-5000, such as 500, 800, 1000, 1200, 1500, 1700, 2000, 3000, 4000 or 5000, preferably having a weight average molecular weight of 600-3000, more preferably having a weight average molecular weight of 700-2000.

Generally, polysiloxane resin is easy to be hard and brittle after film formation. The conventional solution is to add dialkoxysilane (D Type silicone monomer) as a raw material during synthesis, but it is not easy to control D Type silicone The degree of linear polymerization of monomers has limited improvement effects. The inventor of this case found that when (b) the amount of linear polysiloxane oligomer is based on the total weight of non-linear polysiloxane oligomer, linear polysiloxane oligomer and silicone monomer, it is 20wt% to 65wt%, such as 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt% or 65wt%, the properties of the coating composition after curing can be adjusted to have better properties The softness (Softness). According to the present invention, if the amount of linear polysiloxane oligomer is too high (more than 65wt%), it is easy to cause the polysiloxane resin to be too soft and have poor hardness, resulting in insufficient surface strength of the coating film and easy to be scratched; If the amount of linear polysiloxane oligomer is too small (less than 20wt%), it is easy to cause the flexibility of the coating film to deteriorate, and it cannot overcome the defects of the coating film being hard and brittle. The aforementioned amount is preferably 25wt% to 60wt%, more preferably 30wt% to 55wt%.

(c) Silicone monomer According to some embodiments of the present invention, (c) Silicone monomer has the formula (VI): (R ⁸ ) _n Si(OR ⁹ ) _4-n (VI) where: R ⁸ Each independently is H, phenyl, C _1-6 alkyl or has amino, epoxy, vinyl, isocyanate, mercapto or (methyl) ) An organic group of (meth)acryloxy; R ⁹ is a C _1-3 alkyl group, such as methyl, ethyl or propyl; and n is an integer from 0 to 3, such as 0, 1, 2 or 3.

In a preferred embodiment of the present invention, R ^{8 is} each independently H, methyl, ethyl, vinyl, N-(β-aminoethyl)-γ-aminopropyl (N-(β-aminoethyl) -γ-aminopropyl), aminopropyl, γ-glycidoxypropyl, β-(3,4-epoxycyclohexyl) ethyl (β-(3,4-epoxycyclohexyl) ) ethyl), 3-(methacryloyloxy)propyl or mercapto propyl, and R ^{9 is} each independently methyl or ethyl.

According to a preferred embodiment of the present invention, (c) the siloxane single system is selected from the group consisting of the following compounds: trimethylmethoxysilane, trimethylethoxysilane , Dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane Methyltripropoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane ( γ-glycidoxypropyltrimethoxysilane), γ-glycidoxypropyltriethoxysilane (γ-glycidoxypropyltriethoxysilane), γ-glycidoxypropyltriethoxysilane ((γ-glycidoxypropyl)methyldimethoxysilane), γ- Glycidoxypropyl methyldiethoxysilane ((γ-glycidoxypropyl)methyldiethoxysilane), β-(3,4-epoxycyclohexyl) ethyl trimethoxysilane (β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane), 3-(methacryloyloxy)propyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane Silane (N-(β-aminoethyl)-γ-aminopropyl methylbimethoxysilane), N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane (N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane), γ -Aminopropylmethyldiethoxysilane (γ-aminopropylmethyldiethoxysilane), γ-aminopropyltriethoxysilane (γ-aminopropyltriethoxysilane), γ-aminopropyltrimethoxysilane (γ-aminopropyltrimethoxysilane), γ- Sulfhydryl Gamma-mercaptopropyltrimethoxysilane and combinations thereof.

According to some embodiments of the present invention, (c) the amount of siloxane monomer is based on the total weight of the non-linear polysiloxane oligomer, linear polysiloxane oligomer and siloxane monomer, which is 30wt% to 75wt%, such as 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt% or 75wt%, preferably 35% to 70wt%, more preferably 40wt % To 65wt%.

(d) Other components According to some embodiments of the present invention, silica can be added as an inorganic component when preparing the polysiloxane resin, and silica can participate in the polymerization reaction. When the amount of silicon dioxide is 1wt% to 30wt% based on the total weight of nonlinear polysiloxane oligomers, linear polysiloxane oligomers and silicone monomers, the polysiloxane can be further strengthened. The hardness of the resin. The aforementioned amount is preferably 5wt% to 25wt%, more preferably 8wt% to 20wt%.

Preparation of Polysiloxane Resin The polysiloxane resin of the present invention is prepared separately or obtained (a) nonlinear polysiloxane oligomer and (b) linear polysiloxane oligomer, and then ( a) Non-linear polysiloxane oligomer, (b) linear polysiloxane oligomer and (c) siloxane monomer are prepared after reacting as raw materials. Without exceeding the purpose of the present invention, other compounds can also be added as raw materials.

The above-mentioned (a) non-linear polysiloxane oligomer and (b) linear polysiloxane oligomer can be synthesized by oneself or obtained from commercial products.

According to some embodiments of the present invention, the above-mentioned (a) non-linear polysiloxane oligomer, and (b) linear polysiloxane oligomer, or the polysiloxane resin of the present invention is composed of sol-gel (sol-gel) method. In a typical sol-gel method, the reactants will undergo a series of hydrolysis and polymerization reactions to form a colloidal suspension, and the substances in it will condense into a new phase—a solution containing solid polymer, which is called a gel. The properties of the prepared sol-gel are affected by the type of raw material, the type and concentration of the catalyst, the pH value, the temperature, the content, type and concentration of the solvent.

According to some embodiments of the present invention, in the aforementioned synthesis step, a solvent may be added as needed, including but not limited to water, alcohols, ether alcohols or mixtures thereof, such as water, ethylene glycol monobutylether (BCS) , Ethylene glycol monoethyl ether acetate (CAC), ethylene glycol monoethyl ether (ECS), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether Acetate (propylene glycol monomethyl ether acetate, PMA), propylene glycol methyl ether propionate (PMP), or a mixture of the above two.

Generally, polysiloxane resin is easy to be hard and brittle after film formation. The conventional solution is to add dialkoxysilane (D Type silicone monomer) as a raw material during synthesis, but it is not easy to control D Type silicone The degree of linear polymerization of monomers has limited improvement effects. There is also a scheme of mixing organic components into polysiloxane resins to increase its flexibility, but organic components have the disadvantage of poor heat resistance. In addition, hardness and flexibility generally conflict with each other. Therefore, if the general resin has high hardness, the flexibility is usually poor; the flexibility is good, and the hardness is mostly not high. Even though it is known that the properties of the resulting resin can be adjusted by adding linear monomers during synthesis, it is difficult to predict how to make the resin have both excellent hardness and flexibility.

The inventor of this case discovered that the pre-synthesized (a) nonlinear polysiloxane oligomer and (b) linear polysiloxane oligomer with (c) siloxane monomer were used as raw materials, and the component (a) , (B) and (c), the polysiloxane resin obtained by the mutual matching of the three has a synergistic effect. The coating film formed by it has good compactness, high strength but not hard and brittle, and can absorb greater stress and Withstand the volumetric deformation caused by the temperature rise and fall, and the coating surface can remain flat without cracking at high temperatures, which has a wider range of applications. Part of the specific implementation aspects are described in detail. Component (a) can control the structure of the polysiloxane resin to make it tough and rigid, so that the surface of the coating can be kept flat without cracking. The component (a) b) Provide the softness of polysiloxane resin, which can make the coating have bending resistance. Component (a) and component (b) can make the coating have good flexibility. Sub (c) provides the main structure and hardness of the polysiloxane resin. In addition, if the component (a) selects an organic group having a vinyl group, an epoxy group or an acrylic group, the polysiloxane resin can be further cross-linked. By selecting the molecular weight of the oligomer and the content of the aforementioned three components, the molecular weight and polydispersity index (PDI) of the polysiloxane resin can be adjusted.

The polysiloxane resin of the present invention has both hardness, rigidity, flexibility, bending resistance, heat resistance, weather resistance, solvent resistance and chemical resistance. It has good storage stability, so it can be applied to metals Coil intermediate layer or top coat, glass substrate coating, or solar backplane coating. In particular, the metal coil is bent during storage and application. The polysiloxane resin of the present invention has good mechanical properties and flexibility, and can withstand the stress generated during bending without cracking or breaking. In addition, the polysiloxane resin of the present invention has excellent heat resistance and flexibility, so it can be applied to high temperature environments, especially where high temperature resistant coatings are required. For example, the manufacturing process of metal coils often requires a high temperature environment of 200°C to 300°C, and the polysiloxane resin of the present invention can withstand the aforementioned high temperature process.

II. Coating composition containing polysiloxane resin The coating composition of the present invention contains the polysiloxane resin described above. Based on the total weight of the composition, the content of the polysiloxane resin is 1wt% to 99wt%, such as 1wt%, 3wt%, 5wt%, 8wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 90wt% or 99wt%, preferably between 5wt% to 70wt%, more preferably 7wt% to 50wt%.

The coating composition of the present invention may optionally contain any additives known to those with ordinary knowledge in the technical field of the present invention, such as but not limited to inorganic particles, pigments, fillers, hardeners, hardener accelerators, ultraviolet absorbers, Antistatic agent, matting agent, stabilizer, heat dissipation aid, photocatalyst or anti-floating agent, etc.

According to some embodiments of the present invention, the coating composition may optionally include inorganic particles. According to a preferred embodiment of the present invention, the inorganic particles include titanium dioxide, zirconium oxide, silicon dioxide, zinc oxide, strontium titanate, indium tin oxide, antimony tin oxide, lanthanum hexaboride, tungsten oxide, or a combination thereof. The polysiloxane resin and the inorganic particles as appropriate can be mixed in a solvent, and then directly coated on the substrate, and the coating is formed after heat treatment. There are no special restrictions on the order and time of addition of inorganic particles, that is, each component can be mixed with the polysiloxane resin at one time, in batches or in any order, and can be added or added to the polysiloxane resin during the preparation of the polysiloxane resin. The silicone resin is added after preparation to give the coating the desired properties. If added, the content of inorganic particles is 1 wt% to 70 wt%, preferably 5 wt% to 60 wt%, based on the total weight of the solid content of the coating composition.

If the substrate is exposed to an outdoor environment for a long time, it is easy to accumulate moisture and dirt in the environment, resulting in an unclean appearance or poor light utilization. Therefore, according to a preferred embodiment of the present invention, inorganic particles with a photocatalytic effect, such as titanium dioxide, can be added to the coating composition of the present invention and coated on a substrate (such as a metal substrate or a glass substrate for construction) A top coat is formed on the surface to provide a self-cleaning function and reduce labor maintenance costs.

According to some embodiments of the present invention, the coating composition may optionally include photocatalyst particles, such as anatase-type titanium dioxide, zinc oxide, tin oxide, zirconium oxide, zinc sulfide, and cadmium sulfide. The particle size may be 5 nm to 100 nm, if necessary When added, based on the total weight of the solid content of the coating composition, it is 5wt% to 70wt%, preferably 10wt% to 60wt%, more preferably 20wt% to 40wt%.

The solvent that can be used in the coating composition of the present invention is not limited in principle, and may be an appropriate solvent known to those with ordinary knowledge in the technical field of the present invention, such as, but not limited to, water, alcohols, benzene, Ethers, esters, ketones or combinations thereof. Non-limiting examples of alcohol solvents include methanol, ethanol, propanol, butanol, isobutanol, or the like. Non-limiting examples of benzene-based solvents include benzene, toluene, o-xylene, meta-xylene, p-xylene, trimethylbenzene, or styrene or the like. Non-limiting examples of ether solvents include propyl ether, butyl ether, ethylene glycol methyl ether, propylene glycol methyl ether, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate, diethylene glycol butyl ether acetate ( Diethylene glycol butyl ether acetate) or other analogs. Non-limiting examples of ester solvents include, for example, ethyl acetate, butyl acetate, diethyl carbonate, ethyl formate, methyl acetate, ethoxyethyl acetate, ethoxypropyl acetate or monomethyl ether Propylene glycol ester or other similar. Non-limiting examples of ketone solvents include acetone, methyl ethyl ketone or methyl isobutyl ketone or other similar.

Among the conventional methods of preparing coatings, the physical vapor deposition method has the disadvantage of expensive equipment. Although the chemical vapor deposition method has the advantages of being fast and cheap, the formed film has poor wear resistance. In contrast, the coating composition of the present invention adopts the sol-gel method to prepare polysiloxane resin, and the obtained coating composition can be directly coated on the substrate, so it is not only low cost, good production speed, suitable for continuous production, but also The replacement of chemical precursors is relatively simple. The coating method used in the present invention can be any person with ordinary knowledge in the technical field of the present invention, such as but not limited to: knife coating, roller coating, microgravure printing Coating (micro gravure coating), flow coating (flow coating), dip coating (dip coating), spray coating (spray coating), slot die coating, spin coating And curtain coating. According to some embodiments of the present invention, the coating composition can be coated on the substrate by roller coating or spray coating. According to some embodiments of the present invention, the effect of coating the substrate on both sides at the same time can be achieved by the impregnation pulling method.

III. Application of polysiloxane resin and / or coating composition According to some embodiments of the present invention, the polysiloxane resin or coating composition of the present invention can be coated on a substrate for protection, scratch resistance, Impact resistance, weather resistance, reflection, heat insulation or cleaning purposes. The above-mentioned substrates are, for example, but not limited to: metal substrates, plastic substrates, glass substrates or solar backplanes. The type of the metal substrate is not particularly limited, and may be steel, aluminum, or alloy materials, for example. The type of the above-mentioned plastic substrate is not particularly limited. For example, it may be selected from the following group: polyester resin, such as polyethylene terephthalate (PET) or polyethylene naphthalate (polyethylene naphthalate, PEN), polyacrylate resin, such as polymethyl methacrylate (PMMA), polyolefin resin, such as polyethylene (PE) or polypropylene ( polypropylene, PP), polycycloolefin resin, polyimide resin, polycarbonate resin, polyurethane resin, triacetate cellulose triacetyl cellulose (TAC), polylactic acid (polylactic acid), polyvinyl chloride (polyvinyl chloride) and combinations thereof, but not limited to this. The plastic substrate is preferably selected from polyester resins, polycarbonate resins and combinations thereof, more preferably polyethylene terephthalate.

The polysiloxane resin of the present invention has properties such as hardness, rigidity, flexibility, bending resistance, weather resistance, solvent resistance, heat resistance, etc., and can be combined with different additives to make a coating composition as needed. The polysiloxane resin or coating composition of the present invention is suitable for various applications, especially applications requiring a variety of the above properties at the same time, and can be used as an intermediate layer or topcoat for metal coils, coatings for glass substrates, or coatings for solar backplanes .

According to some embodiments of the present invention, the coating composition of the present invention can be used as a top coat or an intermediate layer of metal coils. The substrate used for the metal coil may be, for example, but not limited to: the aforementioned steel, aluminum, or alloy material and other metal substrates. As mentioned earlier, metal coils are bent during storage and application; in addition, if the topcoat contains photocatalyst particles (such as anatase titanium dioxide), the oxidation characteristics of the photocatalyst can easily cause the underlying coating (such as color) Paint layer or base coat) deterioration [1. Does the color paint base coat refer to the same layer? The color paint does not necessarily have to be the base coat? Please confirm whether the modification is appropriate], which will cause the coating to peel off and affect the color rendering effect and photocatalyst effect. The general solution to this problem is to insert a photocatalyst-free intermediary layer between the photocatalyst layer (that is, the topcoat layer) and the coating underneath. Provide good interlayer adhesion between the layer and the coating underneath, and it should be able to reduce the interface stress between different layers due to bending; only if the resin used in the photocatalyst layer and the intermediate layer are different, it will increase the processing complexity . The polysiloxane resin of the present invention has properties such as hardness, rigidity, flexibility, bending resistance and heat resistance. Therefore, the coating composition made of the polysiloxane resin of the present invention can be directly applied to form The photocatalyst topcoat is used as a surface coating to achieve the beneficial effects of self-cleaning the surface of metal coils and reduce labor maintenance costs. It can also be used as an intermediate layer to effectively extend the life of the color paint layer or primer coating and maintain the photocatalyst effect.

According to some embodiments of the present invention, the coating composition of the present invention can be used as a topcoat layer or an intermediate layer. As shown in FIG. 1, an intermediate layer 30 and a topcoat layer 40 are sequentially coated on the substrate 10, and a silicone modified polyester layer 20 (silicone modified polyester layer) may be coated on the substrate before the intermediate layer 30 is coated. , SMP). The intermediate layer 30 and the topcoat layer 40 can use the same or different polysiloxane resins. The intermediate layer 30 can effectively absorb the interface stress generated by the temperature difference during processing. Compared with the intermediate layer 30, the topcoat layer 40 is a surface protective coating, and other additives such as titanium dioxide photocatalyst can be added as needed to form a photocatalyst topcoat. According to a preferred embodiment of the present invention, the substrate 10 can be a metal substrate or a glass substrate, and the interposer 30 and the topcoat layer 40 can use the same polysiloxane resin.

As far as the glass substrate is concerned, the glass substrate itself has shortcomings such as being fragile and not resistant to impacts. When the glass substrate is impacted, it is not only easily damaged and broken, but glass shards are more likely to splash around. When the coating composition of the present invention is applied to a glass substrate, it can form a glass rigid paint, and because of its flexibility, it can provide sufficient protection and reduce the phenomenon of glass chipping. In addition, the glass substrate can achieve the effect of coating the substrate on both sides at the same time by the impregnation and pulling method as described above, so it has the advantage of easy processing.

According to some embodiments of the present invention, the coating composition of the present invention can be used for solar backsheets to protect and support cells, and has good insulation, water resistance, weather resistance, and aging resistance. In addition, the coating composition of the present invention may optionally add light-reflecting substances (such as titanium dioxide TiO ₂ ) to improve the light-reflecting efficiency, so as to increase the utilization rate of sunlight.

Examples The following examples are used to further illustrate the present invention, but not to limit the scope of the present invention. Any modifications and changes that can be easily achieved by a person with ordinary knowledge in the relevant technical field are included in the scope of the disclosure of the specification of this case and the scope of the attached patent application.

(a) Preparation of non-linear polysiloxane oligomer ( oligomer A) TE-24 synthesis Weigh 1652 parts by weight of phenyltrimethoxysilane, 4458 parts by weight of methyltriethoxysilane, and 687 parts by weight Water and 6120 parts by weight of ethyl acetate were stirred in the reaction kettle, and then a mixed aqueous solution of 1067 parts by weight of water and 77 parts by weight of hydrochloric acid (concentration 36.5 wt%) was added dropwise, and then the temperature was raised to 65° C. and reacted at a constant temperature for 1 hour. Then 500 parts by weight of γ-glycidoxypropyltrimethoxysilane were added dropwise, and then the temperature was raised to 77°C and reacted at a constant temperature for 4 hours, and then reduced to room temperature and diluted with ethyl acetate and water, and then sodium carbonate was added to adjust to pH=7 (tested with litmus paper). Then add water into the solution, stir and stand to separate layers, remove the water layer, and repeat three times. Finally, add anhydrous magnesium sulfate to the solution and stir to disperse, and filter with filter paper to remove the magnesium sulfate, you can get TE-24 polysiloxane oligomer A ethyl acetate solution, the solid content is about 50wt%, the molecular weight is about 1558.

OT-24 synthesis weigh 537 parts by weight of phenyltrimethoxysilane, 1455 parts by weight of methyltriethoxysilane, 223 parts by weight of water and 2001 parts by weight of ethyl acetate, stir in the reactor, and then drop 27 parts by weight A mixed aqueous solution of water and 279 parts by weight of hydrochloric acid (concentration 36.5wt%), then heated to 77°C and reacted at a constant temperature for 4 hours. During the reaction, the alcohol and ester solvents were distilled off, and then lowered to room temperature and ethyl acetate and ethyl acetate were added. Dilute with water, then add sodium carbonate to adjust to pH=7 (tested with litmus paper). Then add water into the solution, stir and stand to separate layers, remove the water layer, and repeat three times. Finally, add anhydrous magnesium sulfate to the solution and stir to disperse, and filter the magnesium sulfate with filter paper to remove the magnesium sulfate to obtain the poly OT-24 silicone oligomer A ethyl acetate solution with a solid content of about 50% by weight and a molecular weight of about 10292.

OTM-24 Synthesis Weigh 496 parts by weight of phenyltrimethoxysilane, 1337 parts by weight of methyltriethoxysilane, 206 parts by weight of water and 1836 parts by weight of ethyl acetate, stir in the reaction vessel, and then add 320 parts by weight. A mixed aqueous solution of water and 23 parts by weight of hydrochloric acid (concentration 36.5wt%), heated to 65°C and reacted at a constant temperature for 1 hour, then 52 parts by weight of hexamethyldisiloxane were added dropwise, and then heated to 77°C and reacted at constant temperature 4 After hours, the alcohol and ester solvents were distilled off during the reaction, then reduced to room temperature and diluted with ethyl acetate and water, and then sodium carbonate was added to adjust to pH=7 (tested with litmus paper). Then add water into the solution, stir and stand to separate layers, remove the water layer, and repeat three times. Finally, add anhydrous magnesium sulfate to the solution and stir to disperse, and filter with filter paper to remove the magnesium sulfate, you can get OTM-24 polysiloxane oligomer A ethyl acetate solution, the solid content is about 50wt%, the molecular weight is about 6484.

TM-03 synthesis weighs 380 parts by weight of methyltriethoxysilane, 29 parts by weight of hexamethyldisiloxane, 152 parts by weight of water, 152 parts by weight of alcohol and 1369 parts by weight of ethyl acetate and stirs for reaction Then, add 190 parts by weight of water and 18 parts by weight of hydrochloric acid (concentration 36.5wt%) pre-mixed aqueous solution, then heat to 77°C and react at constant temperature for 4 hours. During the reaction, the alcohol and ester solvents are distilled out, and then reduced Add ethyl acetate and water to dilute to room temperature, then add sodium carbonate aqueous solution to adjust to pH=7 (tested with litmus paper). Then add water into the solution, stir and stand to separate layers, remove the water layer, and repeat three times. Finally, add anhydrous magnesium sulfate to the solution and stir to disperse, and filter with filter paper to remove the magnesium sulfate, that is, TM-03 can obtain polysiloxane oligomer A ethyl acetate solution, the solid content is about 50wt%, and the molecular weight is about 3103.

< Preparation of polysiloxane resin > Respectively mix oligomer A, oligomer B (Dow Corning 3074), silicone monomer and propylene glycol methyl ether acetate (PMA) according to the proportions shown in Tables 1 to 3 (Gram weight) Pour into the glass reactor, then add the silicon dioxide solution (Nissan Snowtex-o solid content 20wt%), citric acid and water into the reactor, then stir and heat to 80°C and react at a constant temperature for 6 hours. Then, ethylene glycol monobutyl ether (BCS) was added and the reaction was continued at 80°C for 2 hours, and then lowered to room temperature to prepare Examples 1 to 7 and Comparative Examples 1 to 9.

Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Silicone monomer Tetraethoxysilane 24.3 24.3 24.3 24.3 24.3 24.3 48.6 Methyltrimethoxysilane 85.1 85.1 85.1 85.1 85.1 85.1 106.4 γ-glycidoxypropyl trimethoxysilane 54.3 54.3 54.3 54.3 54.3 54.3 54.3 Total weight of siloxane monomer 163.7 163.7 163.7 163.7 163.7 163.7 209.3 Oligomer B Dow Corning 3074 193.9 193.9 193.9 193.9 193.9 162 113.4 Oligomer A OT-24 solution (50wt%) 0 0 0 0 0 0 0 OTM-24 solution (50wt%) 0 0 0 0 0 0 0 TE-24 solution (50wt%) 6.8 17 34 54.4 74.8 0 8.5 TM-03 solution (50wt%) 0 0 0 0 0 11.6 0 Total weight of oligomer A 3.4 8.5 17 27.2 37.4 5.8 4.25 PMA 56.5 56.5 56.5 56.5 56.5 91.3 135 Citric acid 3.15 3.15 3.15 3.15 3.15 3.15 3.15 Silica solution (20wt%) 240.5 240.5 240.5 240.5 240.5 240.5 240.5 H ₂ O 34.02 34.02 34.02 34.02 34.02 29.02 0 BCS 229.3 229.3 229.3 229.3 229.3 100 159.3 gross weight 927.87 938.07 955.07 975.47 995.87 801.27 869.15 Oligomer A+oligomer B+silicone monomer 361 366.1 374.6 384.8 395 331.5 326.95 Proportion of oligomer A* (wt%) 0.94% 2.32% 4.54% 7.07% 9.47% 1.75% 1.30% Proportion of oligomer B*(wt%) 53.71% 52.96% 51.76% 50.39% 49.09% 48.87% 34.68% Proportion of siloxane monomer*(wt%) 45.35% 44.71% 43.70% 42.54% 41.44% 49.38% 64.02% *Based on the total weight of oligomer A (non-linear polysiloxane oligomer) + oligomer B (linear polysiloxane oligomer) + silicone monomer

Table 2 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 Comparative example 9 Silicone monomer Tetraethoxysilane 48.6 48.6 24.3 24.3 24.3 24.3 9.4 47.65 15.04 Methyltrimethoxysilane 106.4 106.4 85.1 85.1 85.1 85.1 32.97 166.87 52.7 γ-glycidoxypropyl trimethoxysilane 54.3 54.3 54.3 54.3 54.3 54.3 21.04 47.6 33.6 Total weight of siloxane monomer 209.3 209.3 163.7 163.7 163.7 163.7 63.41 262.12 101.34 Oligomer B Dow Corning 3074 113.4 113.4 193.9 0 193.9 0 162 36.6 256.3 Oligomer A OT-24 solution (50wt%) 8.5 0 0 0 0 0 0 0 0 OTM-24 solution (50wt%) 0 8.5 0 0 0 0 0 0 0 TE-24 solution (50wt%) 0 0 1.785 0 0 17 106.08 17 17 TM-03 solution (50wt%) 0 0 0 0 0 0 0 0 0 Total weight of oligomer A 4.25 4.25 0.8925 0 0 8.5 53.04 8.5 8.5 PMA 135 135 56.5 56.5 56.5 56.5 91.3 56.5 56.5 Citric acid 3.15 3.15 3.15 3.15 3.15 3.15 3.15 3.15 3.15 Silica solution (20wt%) 240.5 240.5 240.5 120 240.5 120 240.5 240.5 240.5 H ₂ O 0 0 34.02 34.02 34.02 34.02 29.02 34.02 34.02 BCS 159.3 159.3 229.3 229.3 229.3 229.3 100 229.3 229.3 gross weight 869.15 869.15 922.855 606.67 921.07 623.67 795.46 879.19 938.11 Oligomer A+oligomer B+silicone monomer 326.95 326.95 358.493 163.7 357.6 172.2 278.45 307.2 366.14 Proportion of oligomer A* (wt%) 1.30% 1.30% 0.25% 0.00% 0.00% 4.94% 19% 2.7% 2.3% Proportion of oligomer B*(wt%) 34.68% 34.68% 54.09% 0.00% 54.22% 0.00% 58.2% 12% 70% Proportion of siloxane monomer*(wt%) 64.02% 64.02% 45.66% 100.00% 45.78% 95.06% 22.7% 85.3% 27.7% *Based on the total weight of oligomer A (non-linear polysiloxane oligomer) + oligomer B (linear polysiloxane oligomer) + silicone monomer

< Physical property test > The resin prepared in the above examples and comparative examples was diluted with PMA to a solid content of about 15wt%, and coated with a No. 8 coating bar on the sandpaper polished tinplate (7*14cm), coating thickness about 18μm, after baking for 30 minutes to 200 ^o C, a coating thickness of approximately 2.7μm is formed.

Carry out various tests, including flexibility, transparency, chemical resistance (solvent resistance, acid resistance and alkali resistance), adhesion, collision test and pencil hardness. The details of each test are as follows: Solvent resistance: alcohol , Xylene and methyl ethyl ketone (methyl ethyl ketone) are wiped back and forth (counted as 1 time) in the wet state, and observe whether there is any damage every 50 times. Record the number of wipes before damage occurs. Acid resistance: Do a spot test with a 5wt% hydrochloric acid solution in a wet state, and observe whether the coating is damaged or not; "○" indicates that the coating color of the test area has no color difference with the surrounding non-test area coating, and "△" indicates that the test area is coated The color of the layer changes slightly, and there is a color difference with the coating in the surrounding non-test area. "╳" means that the coating in the test area is completely bitten and the substrate is directly exposed. Alkali resistance: use a 5wt% sodium hydroxide solution in a wet state to conduct a spot test, and observe whether the coating is damaged or not. The judgment method is the same as the description of acid resistance. Adhesion: 100 grid test, 3M Scotch 600 tape. Pencil hardness: Use a Mitsubishi standard hardness test pencil to test the hardness of the coating under a load of 1 kg. Impact resistance test: Use an impact testing machine (made by Jinliang Industrial Co., Ltd.) to make the impact head at the bottom of the hammer (the diameter of the impact head is 3/16") contact the substrate, and set a weight 0.5m above the top of the hammer. A 1kg drop hammer makes the drop hammer fall in a free fall to hit the hammer, and then the impact head hits the substrate. The substrate is coated with the coated side as the front side, and the uncoated side is the reverse side; after the impact, the naked eye Observe whether the coating is damaged or not. T-bending test: Coating the coating composition prepared above on an iron sheet, at a temperature of 180°C, reacting for 30 minutes to cure, and the thickness of the coating film is about 20μm. The iron sheet of the coating composition is T-bend (T-bend) according to the test method of JIS-H4001-67.45. The first fold represents 0T, the second fold represents 1T, and so on, the less T represents the more flexible Good. High-temperature baking surface cracking situation: The resin prepared in the examples and comparative examples was diluted with PMA to a solid content of about 15wt%, and coated with a No. 8 coating bar on the sandpaper polished tinplate (7*14cm) , The coating thickness is about 18μm, and then ^{bake at 300 o} C for 45 seconds. After returning to room temperature, observe whether the coating surface is cracked with a magnifying glass magnification of 15 times; "△" means that no cracks are observed with the naked eye but the cracks are observed with a magnifying glass magnification of 15 times, and "╳" means that the cracks are observed with the naked eye. The results of each test are listed in Tables 3 and 4.

table 3 Physical properties Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Film thickness (μm) ~2.7µm ~2.7µm ~2.7µm ~2.7µm ~2.7µm ~2.7µm ~2.7µm Pencil hardness ＞4H ＞4H 8H 8H 7H ＞4H 4H Adherence (100 grids) 100/100 100/100 100/100 100/100 100/100 100/100 100/100 Acid resistance (HCl) (5wt%), point test ○ ○ ○ ○ ○ ○ ○ Alkali resistance (NaOH) (5wt%), point test ○ ○ ○ ○ ○ ○ △ Solvent resistance (number of passes through wiping back and forth) alcohol 300 300 300 300 300 250 300 Xylene 300 300 200 200 200 100 300 Butanone 100 300 200 250 200 150 300 Impact resistance (1kg/0.5m) front (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass Negative (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass T-bend 0~1T 0~1T 0~1T 0~1T 0~1T 0~1T 0~1T High temperature baking surface cracking condition △ ○ ○ ○ ○ ○ ○

Table 4 Physical properties Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 Comparative example 9 Film thickness (μm) ~2.7µm ~2.7µm ~2.7µm ~2.7µm ~2.7µm ~2.7µm ~2.7µm ~2.7µm ~2.7µm Pencil hardness ＞4H ＞4H ＞4H ＞4H 3H ＞5H ＞4H ＞4H 3H Adherence (100 grids) 100/100 100/000 100/100 100/100 100/100 100/100 100/000 100/100 100/100 Acid resistance (HCl) (5wt%), point test △ △ △ ╳ ○ △ ○ ○ ○ Alkali resistance (NaOH) (5wt%), point test △ △ ○ ╳ ○ △ ╳ ╳ ○ Solvent resistance (number of passes through wiping back and forth) alcohol 300 300 200 300 200 300 300 300 300 Xylene 300 300 250 300 250 300 50 300 100 Butanone 300 300 100 300 50 250 50 300 200 Impact resistance (1kg/0.5m) front (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass Negative (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass (3/16")pass T-bend 0~1T 0~1T 0~1T 1~2T 0~1T 1~2T 0~1T 1~2T 0~1T High temperature baking surface cracking condition ╳ ╳ ╳ ╳ ╳ ╳ ╳ ╳ ╳

It can be seen from the results that Examples 1 to 7 use (a) nonlinear polysiloxane oligomers, which have a molecular weight of 500-6000, (b) linear polysiloxane oligomers, and (c) silicone oligomers. Monomer, the prepared resin has good physical properties, such as hardness, adhesion, acid resistance, alkali resistance, solvent resistance, impact resistance, flexibility, high temperature baking resistance, etc.

In contrast, Comparative Example 1 uses OT-24 with a molecular weight of about 10292 as (a) nonlinear polysiloxane oligomer components; Comparative Example 2 uses OTM-24 with a molecular weight of about 6484 as (a) Non-linear polysiloxane oligomer component; Comparative Example 3 uses a low content of (a) non-linear polysiloxane oligomer; Comparative Example 4 does not use (a) non-linear polysiloxane oligomer and (b) Linear polysiloxane oligomer; Comparative Example 5 did not use (a) Non-linear polysiloxane oligomer; Comparative Example 6 did not use (b) Linear polysiloxane oligomer; comparison Example 7 uses high content (a) non-linear polysiloxane oligomer; Comparative Example 8 uses low content (b) linear polysiloxane oligomer; Comparative Example 9 uses high content (b) linear polysiloxane For the silicone oligomer, the physical properties obtained in the above-mentioned comparative example are inferior.

10: substrate 20: Polysiloxane modified polyester layer 30: Intermediary layer 40: top coat

Figure 1 is a schematic diagram of the polysiloxane resin or coating composition of the present invention applied to a substrate.

10: substrate

20: Polysiloxane modified polyester layer

30: Intermediary layer

40: top coat

Claims (12)

A polysiloxane resin comprising the reaction product of the following: (a) Non-linear polysiloxane oligomer, which has a C _1-3 alkoxy group or a hydroxyl group, and has a weight average of about 500-6000 Molecular weight, where the (a) nonlinear polysiloxane oligomer has the formula (I): (R ⁵ ₃ SiO _1/2 ) _x (R ⁶ SiO _3/2 ) _y (R ⁷ O _1/2 ) _z (I), wherein R ⁵ and R ⁶ are each independently a methyl group, a phenyl group, or a monovalent organic group having an epoxy group or an acrylic group, and R ⁷ is a C _1-3 alkyl group or H; each R ⁵ May be the same or different, each R ⁶ may be the same or different, each R ⁷ may be the same or different; x≧0, y>0, z>0; and x/y is any value ranging from 0 to 10; (b ) Linear polysiloxane oligomer, which has the formula (II):

Wherein each R ³ may be the same or different, and each is independently a methyl group or a phenyl group; each R ⁴ may be the same or different, and each is independently H, a methyl group or an ethyl group; and m is an integer from 2 to 20; and (c) Silicone monomer. The polysiloxane resin of claim 1, wherein the (b) linear polysiloxane oligomer has a weight average molecular weight of 500-5000. The polysiloxane resin according to claim 1, wherein the (a) non-linear polysiloxane oligomer comprises a structural unit derived from a silicone monomer of formula (III):

Wherein, each R ¹ may be the same or different, and each independently is a C _1-3 alkyl group; each R ⁶ may be the same or different, and each independently is a methyl group, a phenyl group, or an organic group with an epoxy group or an acrylic group . The polysiloxane resin according to claim 1, wherein the (a) nonlinear polysiloxane oligomer comprises a silicone monomer derived from formula (III) and formula (IV) or formula (V) The structural unit of siloxane monomer:

(R ⁵ ) ₃ Si-O-Si(R ⁵ ) ₃ (IV)

Among them: each R ¹ may be the same or different, and each independently is a C _1-3 alkyl group; each R ⁶ may be the same or different, and each independently is a methyl group, a phenyl group, or an organic group with an epoxy group or an acrylic group ; Each R ⁵ may be the same or different, and each independently is a methyl group, a phenyl group, or an organic group with an epoxy group or an acrylic group; and each R ⁸ may be the same or different, and each independently is a C _1-3 alkoxy group基 or -Cl. Such as the polysiloxane resin of claim 1, wherein the amount of the (a) non-linear polysiloxane oligomer is non-linear polysiloxane oligomer, linear polysiloxane oligomer and silicone Total weight of monomer In total, it is 0.5wt% to 15wt%. Such as the polysiloxane resin of claim 1, wherein the (b) linear polysiloxane oligomer is used in the amount of non-linear polysiloxane oligomer, linear polysiloxane oligomer and silicone monomer The total weight of the body is 20wt% to 65wt%. Such as the polysiloxane resin of claim 1, wherein the amount of the (c) siloxane monomer is a total of nonlinear polysiloxane oligomers, linear polysiloxane oligomers and siloxane monomers By weight, it is 30wt% to 75wt%. Such as the polysiloxane resin of claim 1, wherein the (c) siloxane single system is selected from the group consisting of the following compounds: trimethylmethoxysilane, trimethylethoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, tetraethoxysilane, vinyl trimethoxysilane Silane, vinyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl methyldimethoxy Methyl silane, γ-glycidoxypropyl methyl diethoxy silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-(methacryloxy) propyl trimethyl Oxyoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-amine Propylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and combinations thereof. A coating composition comprising the polysiloxane tree according to any one of claims 1 to 8 fat. The coating composition according to claim 9, further comprising inorganic particles. A use of the polysiloxane resin according to any one of claims 1 to 8 or the coating composition according to any one of claims 9 to 10, which is used as an intermediate layer or top coat of a metal coil, glass Coatings for substrates or solar backplanes. A substrate comprising a coating composed of the polysiloxane resin according to any one of claims 1 to 8 or the coating composition according to any one of claims 9 to 10, wherein the substrate is a metal substrate, Glass substrate or solar backplane.

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